期刊论文

Zeng Rong-ying

中文

光谱学与光谱分析

1000-0593

2007

27

7

1271-1275

10.3964/j.issn.1000-0593.2007.07.006

国家自然科学基金项目（29863001）； 湖南省教育厅资助项目（02C136）； 衡阳师范学院启动基金项目资助；

本校为第一且通讯机构

用从头计算(ab initio)方法,在HF/CEP-4G水平上,全优化计算了O_(s3)(CO)_(10)(μ-L1)(μ-L2)[L1,L2=H,Cl,Br,I]簇合物的的分子几何构型,在此基础上对这些簇合物的前线轨道进行了讨论,发现对于M-M键,p轨道虽有贡献,但以s,d轨道的贡献为主,同时从Cl→I,随着桥配体原子序的增大,O_(s3)(CO)_(10)(μ-L)_2类簇合物的HOMO与NHOMO轨道能量依次升高,而O_(s3)(CO)_(10)(μ-H)(μ-L)类簇合物只有HOMO轨道能量依次升高,而O_(s3)(CO)_(10)(μ-L)_2类簇合物的LUMO与HOMO的能量差△_(εL-H)及LUMO与NHOMO的能量差△_(εL-NH)都依次变小,可以预示,簇合物的电子光谱基谱带将红移.用TDHF计算了这些簇合物的电子吸...

Ab initio method was used to optimize the molecular geometry for a series of clusters (μ-L1) (μ-L2)-decacarbonyltri-osmium[L1, L2 = H, Cl, Br, I] at HF/CEP-4G level. The related chemical properties of clusters, in particular, the regularities of the bridge halogen effects on spectroscopic properties and bonding properties were discussed. The calculation results of the frontier molecular orbital showed that M-M bonds were mainly composed of s and d atomic orbitals. From Cl to I, with the atom number of bridge ligand increasing, HOMO and NHOMO orbitals on the Os3 (CO)10 (μ-L)2 clusters ...